The present invention relates to NOx reduction compositions and the method of use thereof to reduce NOx emissions in refinery processes, and specifically in fluid catalytic cracking (FCC) processes. More particularly, the present invention relates to NOx reduction compositions and their method of use to reduce the content of gas phase reduced nitrogen species in FCC regenerator off gases released from a fluid catalytic cracking unit (FCCU) regenerator operating in a partial or incomplete combustion mode.
In recent years there has been an increased concern in the United States and elsewhere about air pollution from industrial emissions of noxious oxides of nitrogen, sulfur and carbon. In response to such concerns, government agencies have in some cases already placed limits on allowable emissions of one or more of the pollutants, and the trend is clearly in the direction of increasingly stringent restrictions.
NOx or oxides of nitrogen, in flue gas streams exiting from fluid catalytic cracking (FCC) regenerators is a pervasive problem. Fluid catalytic cracking units (FCCU) process heavy hydrocarbon feeds containing nitrogen compounds a portion of which is contained in the coke on the catalyst as it enters the regenerator. Some of this coke nitrogen is eventually converted into NOx emissions, either in the FCC regenerator or in a downstream CO boiler. Thus all FCCUs processing nitrogen-containing feeds can have a NOx emissions problem due to catalyst regeneration.
In an FCC process, catalyst particles (inventory) are repeatedly circulated between a catalytic cracking zone and a catalyst regeneration zone. During regeneration, coke from the cracking reaction deposits on the catalyst particles and is removed at elevated temperatures by oxidation with oxygen containing gases such as air. The removal of coke deposits restores the activity of the catalyst particles to the point where they can be reused in the cracking reaction. The coke removal step is performed over a wide range of oxygen conditions. At the minimum, there is typically at least enough oxygen to convert essentially all of the coke made to CO and H2O. At the maximum, the amount of oxygen available is equal to or greater than the amount necessary to oxidize essentially all of the coke to CO2 and H2O.
In an FCC unit operating with sufficient air to convert essentially all of the coke on the catalyst to CO2 and H2O, the gas effluent exiting the regenerator will contain xe2x80x9cexcess oxygenxe2x80x9d (typically 0.5 to 4% of total off gas). This combustion mode of operation is usually called xe2x80x9cfull burnxe2x80x9d. When the FCCU regenerator is operating in full burn mode, the conditions in the regenerator are for the most part oxidizing. That is, there is at least enough oxygen to convert (burn) all reducing gas phase species (e.g., CO, ammonia, HCN) regardless of whether this actually happens during the residence time of these species in the regenerator. Under these conditions, essentially all of the nitrogen deposited with coke on the catalyst during the cracking process in the FCCU riser is eventually converted to molecular nitrogen or NOx and exits the regenerator as such with the off gas. The amount of coke nitrogen converted to NOx as opposed to molecular nitrogen depends on the design, conditions and operation of the FCCU, and especially of the regenerator, but typically the majority of coke nitrogen exits the regenerator as molecular nitrogen.
On the other hand, when the amount of air added to the FCCU regenerator is insufficient to fully oxidize the coke on the cracking catalyst to CO2 and H2O, some of the coke remains on the catalyst, while a significant portion of the burnt coke carbon is oxidized only to CO. In FCCUs operating in this fashion, oxygen may or may not be present in the regenerator off gas. However, should any oxygen be present in the regenerator off gas, it is typically not enough to convert all of the CO in a gas stream to CO2 according to the chemical stoichiometry of
CO+xc2xdO2xe2x86x92CO2
This mode of operation is usually called xe2x80x9cpartial burn.xe2x80x9d When an FCC U regenerator is operating in partial burn mode, the CO produced, a known pollutant, cannot be discharged untreated to the atmosphere. To remove the CO from the regenerator off gas and realize the benefits of recovering the heat associated with burning it, refiners typically burn the CO in the regenerator off gas with the assistance of added fuel and air in a burner usually referred to as xe2x80x9cthe CO boilerxe2x80x9d. The heat recovered by burning the CO is used to generate steam.
When the regenerator is operating in partial burn, the conditions in the regenerator, where the oxygen added with air has been depleted and CO concentration has built up, are overall reducing. That is, there is not enough oxygen to convert/burn all reducing species regardless if some oxygen is actually still present. Under these conditions some of the nitrogen in the coke is converted to so called xe2x80x9cgas phase reduced nitrogen speciesxe2x80x9d, examples of which are ammonia and HCN. Small amounts of NOx may also be present in the partial burn regenerator off gas. When these gas phase reduced nitrogen species are burnt in the CO boiler with the rest of the regenerator off gas, they can be oxidized to NOx which is then emitted to the atmosphere. This NOx along with any xe2x80x9cthermalxe2x80x9d NOx formed in the CO boiler burner by oxidizing atmospheric N2 constitute the total NOx emissions of the FCCU unit operating in a partial or incomplete combustion mode.
FCCU regenerators may also be designed and operated in a xe2x80x9cincomplete burnxe2x80x9d mode intermediate between full burn and partial burn modes. An example of such an intermediate regime occurs when enough CO is generated in the FCCU regenerator to require the use of a CO boiler, but because the amounts of air added are large enough to bring the unit close to full burn operation mode, significant amounts of oxygen can be found in the off gas and large sections of the regenerator are actually operating under overall oxidizing conditions. In such case, while gas phase reduced nitrogen species can still be found in the off gas, significant amounts of NOx are also present. In most cases a majority of this NOx is not converted in the CO boiler and ends up being emitted to the atmosphere.
Yet another combustion mode of operating an FCCU is nominally in full burn with relatively low amounts of excess oxygen and/or inefficient mixing of air with coked catalyst. In this case, large sections of the regenerator may be under reducing conditions even if the overall regenerator is nominally oxidizing. Under these conditions reduced nitrogen species may be found in the regenerator off gas along with NOx.
Various catalytic approaches have been proposed to control NOx emissions in the flue gas exiting from the FCCU regenerator.
For example, recent patents, including U.S. Pat. Nos. 6,280,607, 6,129,834 and 6,143,167, have proposed the use of NOx removal compositions for reducing NOx emissions from an FCCU regenerator. U.S. Pat. No. 6,165,933 also discloses a NOx reduction composition, which promotes CO combustion during an FCC catalyst regeneration process step while simultaneously reducing the level of NOx emitted during the regeneration step. NOx reduction compositions disclosed by these patents may be used as an additive, which is circulated along with the FCC catalyst inventory or incorporated as an integral part of the FCC catalyst.
In U.S. Pat. No. 4,290,878, NOx is controlled in the presence of a platinum-promoted CO oxidative promoter in a full burn combustion regenerator by the addition of iridium or rhodium on the combustion promoter in lesser amounts than the amount of platinum.
U.S. Pat. No. 4,973,399, discloses copper-loaded zeolite additives useful for reducing emissions of NOx from the regenerator of an FCCU unit operating in full CO-burning mode.
U.S. Pat. No. 4,368,057, teaches the removal of NH3 contaminants of gaseous fuel by reacting the NH3 with a sufficient amount of NO.
However, aforementioned prior art has failed to appreciate an FCC process which minimizes the amount of NOx and gas phase reduced nitrogen species, e.g. NH3, HCN, in the flue gas of an FCCU regenerator operating in a partial or incomplete combustion mode.
Efforts to control ammonia released in an FCC regenerator operated in a partial or an incomplete mode of combustion have been known.
For example, U.S. Pat. No. 5,021,144 discloses reducing ammonia in an FCC regenerator operating in a partial burn combustion mode by adding a significant excess of the amount of a carbon monoxide (CO) oxidative promoter sufficient to prevent afterburn combustion in the dilute phase of the regenerator.
U.S. Pat. No. 4,755,282 discloses a process for reducing the content of ammonia in a regeneration zone off gas of an FCCU regenerator operating in a partial or incomplete combustion mode. The process requires passing a fine sized, i.e. 10 to 40 microns, ammonia decomposition catalyst to either the regeneration zone of an FCCU, or an admixture with the off gas from the regeneration zone of the FCCU, at a predetermined make-up rate such that the residence time of the decomposition catalyst relative to the larger FCC catalyst particles will be short in the dense bed of the regenerator due to rapid elutriation of the fine sized ammonia decomposition catalyst particles. The fine sized elutriated decomposition catalyst particles are captured by a third stage cyclone separator and recycled to the regenerator of the FCCU. The decomposition catalyst may be a noble group metal dispersed on an inorganic support.
U.S. Pat. No. 4,744,962 is illustrative of a post-treatment process to reduce ammonia in the FCCU regenerator flue gas. The post-treatment involves treating the regenerator flue gas to lessen the ammonia content after the gas has exited the FCCU regenerator but before passage to the CO boiler.
There remains a need in the refining industry for improved compositions and processes which minimizes the content of gas phase reduced nitrogen species and NOx emitted from a partial or incomplete combustion FCCU regenerator during an FCC process, which compositions are effective and simple to use.
The essence of the present invention resides in the discovery of particulate compositions which are capable of being circulated throughout a fluid catalytic cracking unit (FCCU) along with the cracking catalyst inventory to minimize the content of gas phase reduced nitrogen species, e.g. NH3 and HCN, and NOx present in the off gas of the FCCU regenerator when the FCCU regenerator is operated in a partial or incomplete burn mode. Advantageously, the compositions exhibit high efficiencies for the oxidation of gas phase reduced nitrogen species present in the regenerator off gas to molecular nitrogen prior to passage of the off gas to the CO boiler. This reduced content of gas phase reduced nitrogen species in the off gas provides for an overall reduction of NOx emitted into the atmosphere from the FCCU due to a decrease in the amount of the nitrogen species being oxidized to NOx in the CO boiler as CO is oxidized to CO2.
Despite the reducing environment in an FCCU regenerator operated in a partial bum or incomplete burn mode, some NOx may form in the regenerator. In addition to reducing the content of gas phase reduced nitrogen species, compositions of the invention also enhance the removal of any NOx formed in the partial or incomplete burn regenerator by catalyzing the reaction of NOx with reductants typically found in the FCCU regenerator, e.g. CO, hydrocarbons, and gas phase reduced nitrogen species, to form molecular nitrogen. Advantageously, the compositions of the invention provide a reduction of NOx formed in the regeneration prior to the NOx exiting the regenerator and being passed unabated through the CO boiler into the environment.
In accordance with the present invention, compositions of the invention are comprised of a particulate composition which comprises (i) an acidic metal oxide which contains substantially no zeolite; (ii) an alkali metal, alkaline earth metal, and mixtures thereof, measured as the metal oxide, (iii) an oxygen storage component, and (iv) a noble metal component, preferably platinum, rhodium, iridium or mixtures thereof. In a preferred embodiment of the invention, compositions of the invention are used in the FCC process as separate additives particles circulated along with the circulating FCC catalyst inventory.
The present invention also provides a process for reducing the content of gas phase reduced nitrogen species released from the regenerator of an FCCU operated in a partial or incomplete mode of combustion. In accordance with the present invention, the process comprises contacting under FCC catalytic conditions the off gas of an FCCU regenerator operated in a partial or incomplete combustion mode with an amount of the compositions of the invention effective to oxidize the gas phase reduced nitrogen species to molecular nitrogen. The invention also provides a process for reducing NOx emissions from an FCC process operated in a partial or incomplete combustion modes using the compositions of the invention.
Accordingly, it is an advantage of this invention to provide compositions which are useful to reduce the content of gas phase reduced nitrogen species released from an FCCU regenerator operating in partial or incomplete combustion modes during an FCC process.
It is also an advantage of this invention to provide compositions which are useful to reduce NOx emissions from an FCCU regenerator operating in partial or incomplete combustion modes by minimizing the amount of reduced nitrogen species emitted from the regenerator during an FCC process.
Another advantage of the invention is to provide compositions which are effective to oxidize gas phase reduced nitrogen species released from an FCCU regenerator operating in partial or incomplete combustion modes to molecular nitrogen, thereby minimizing the conversion of the reduced nitrogen species to NOx in the downstream CO boiler.
It is another advantage of this invention to provide compositions which are useful to reduce NOx emissions from an FCCU regenerator operating in partial or incomplete combustion modes to molecular nitrogen by catalyzing the reaction of NOx with CO and other reductants typically present in a partial or incomplete bum FCCU regenerator.
It is another advantage of this invention to provide a process for the reduction of the content of NOx in the off gas of an FCCU regenerator operating in partial or incomplete combustion mode by reducing the content of gas phase reduced nitrogen species being emitted in the off gas released from the regenerator, prior to passage of the gas to a CO boiler, whereby as CO is oxidized to CO2, a lesser amount of the gas phase reduced nitrogen species is oxidized to NOx.
It is another advantage of this invention to provide a process for the reduction of gas phase reduced nitrogen species in an effluent gas stream passed from an FCC regenerator to a CO boiler, whereby as CO is oxidized to CO2 a lesser amount of the reduced nitrogen species is oxidized to NOx.
Another advantage of this invention is to provide a process for the reduction of the content of NOx in the off gas of an FCCU regenerator operating in a partial or incomplete combustion mode by the reduction of NOx being emitted in the off gas released from the regenerator, prior to passage of the gas to the CO boiler where the NOx remains untreated and is eventually released into the environment.
Yet another advantage of this invention is to provide improved partial or incomplete combustion FCC processes using the compositions of the invention.
These and other aspects of the present invention are described in further detail below.